Perfluoroalkyl esters of mercapto- and thio-carboxylic acids

ABSTRACT

Novel perfluoroalkyl group containing mercaptans and sulfides are disclosed having soil repellent properties if applied to substrates such as textiles, paper and leather and being useful as intermediates for the synthesis of soil repellent polymers. The adducts are obtained by the base or free radical catalyzed addition of hydrogen sulfide or mono- or polymercaptans to perfluoroalkyl group containing esters of fumaric, maleic, citraconic, mesaconic, itaconic, methylene malonic or aconitic acid.

United States Patent [191 Falk et al.

[4 1 May 27, 1975 PERFLUOROALKYL ESTERS OF MERCAPTO- AND THIO-CARBOXYLICACIDS [75] Inventors: Robert Allan Falk, New City;

Eduard Karl Kleiner, New York, both of N.Y.

[73] Assignee: Ciba-Geigy Corporation, Ardsley,

[22] Filed: Nov. 17, 1971 [21] Appl. N0.: 199,715

[52] US. Cl 260/481 R; 117/139.5; 260/470;

260/386 [51] Int. Cl. C07c 153/07 [58] Field of Search 260/481 R [56]References Cited UNITED STATES PATENTS 3,172,910 3/1965 Brace 260/481 R3,716,466 2/1973 Hook 260/481 R Primary ExaminerJohn F. TerapaneAttorney, Agent, or F irm-Joseph G. Kolodny; Edward McC. Roberts;Prabodh l. Almaula ABSTRACT citraconic, mesaconic, itaconic, methylenemalonic or aconitic acid.

12 Claims, No Drawings PERFLUOROALKYL ESTERS OF MERCAPTO- ANDTHIO-CARBOXYLIC ACIDS The invention relates to novel mercaptans andsulfides which possess soil repellent properties when applied to varioussubstrates, In addition the novel mercaptans are useful in thereparation of polymers which also are useful for similar applications.The soil repellency finishes are useful to treat materials such astextiles, paper, leather, painted wooden, metallic surfaces and thelike.

The compounds of the present invention are of the following formula:

$ C-Cl f '2 s with the proviso if Z represents H, n will be zero and mwill be 1, or if Z represents R AR C-CH

n will be zero and m will be 1 B is an inert linkage group;

m is l to 10;

n is zero to 9.

When Z equals B and n is a positive integer greater than zero, acompound of the following formula is ob- In contrast if Z represents Bbut n equals zero, the

following is realized:

II R

. f R1 v 20 l wherein R, R and R are hydrogen, methyl, R A or v H-CSRIACHQ with the requirement that at least one or two llq of R, R and Rrepresent RjA orR ACH R is'a peri p I m fluoroalkyl group of 2 to 18carbon atoms and more preferably 6 to 12 carbon atoms; 25 If Zrepresents H, n will be zero, In will be one and AR; is the compoundwill be:

AR its 0 v 0 14 1 i ll x-c H -R i -CX- C K 2 g z P 2D O Rf O CHCHCHC HRC JOCHCHCHCH 14 k 2 f 5 le k 2 T 'p p f -co-c H XC H GHQ-R 0-0 H" H, CH-0 F 4 -R P2P kzk r p2p 2 P p 9 9 COC H X- '-r p 2p C l'lz Cl-l bll Cl-lP COCKHZKCH C l Crl CpF2p O n O O inc-c H on cmfln w 'io-c H CH CH ma 2R k lc "r 14 K 2 Y f or If Z represents the compound is:

R A 1 f /R III =C to hydrogen sulfide (H 5) or monoor polymercaptans ofthe formula:

IV B- sH In formulas III and IV the substituents have been definedpreviously while q is an integer from 1 to 10. (Formula IV) The type ofesters of formula III which may be employed are derived from fumaric,maleic, citraconic, mesaconic, itaconic, methylene malonic, and aconiticacids. The formula III esters are defined to be:

Type Ester R R R Fumarate H AR, I-I Maleate -AR; -l-I H Mesaconate AR,CI-l Citraconate -AR -H -CH ltaconate H --H -CH AR, Methylene malonate H-l-I AR cis-Aconitate -l-I AR; Cl-I AR, trans-Aconitate AR; H CH AR,

In the foregoing formula,-AR; may be for example:

wherein X is oxygen or sulfur, k is zero to 10, I p is 2 to 12,

R is hydrogen or alkyl of 1 to 4 carbons R, is a perfluoroalkyl groupwith 2 to 18 carbons,

straight or branched, and preferably 6 to 12 carbons.

The preparation of perfluoroalkyl containing esters disclosed herein andespecially useful in preparing the novel compounds or adducts of thepresent invention are described in the following copending applicationsassigned to the assignee of the present invention:

Ser. No. 720,370, filed Apr. 10, 1968, in the names of Eduard K. Kleinerand Martin Knell; Ser. No. 732,040, filed May 27, 1968, in the names ofEduard K. Kleiner, Martin Knell and Pier Luigi Pacini now US. Pat. No.3,658,857; Ser. No. 812,439, filed Apr. 1, 1969, in the name of EduardK. Kleiner now US. Pat. No. 3,636,085; Ser. No. 820,647, filed Apr. 30,1969, in the name of Eduard K. Kleiner now US. Pat. No. 3,658,843; andSer. No. 833,706, filed June 16, 1969, in the names of Eduard K. Kleinerand Pier Luigi Pacini now US. Pat. No. 3,645,985.

The disclosure of these copending applications for the preparation ofthe starting esters and the related subject matter is incorporated byreference herein.

Referring to the starting mono or polymercaptans, the formula compoundB-(SHL, is utilized where q is an integer from 1 to 10. Most desirablyfrom the standpoint of the final utility of the invention are the tetrato hexamercaptans. In the above formula B serves as an inert linkagegroup for the SH radical. Thus it will be immediately recognized that awide variety of linkage groups may be employed. SinceB serves as aconnecting bridge to the mercaptan for the initial reactant in formulaIV and as a connecting bridge on the novel adducts of formula I, la, andII, the sole criticality for B is that itremain intact throughout thereaction. In other words B is not considered to be reactive in formulaI, Ia, II and IV and will be an inert portion.

The following mono and polymercaptans are considered illustrative of thelinkage group B where B, B

F K 2k co c a cmca cH 0 2p 0 R H -X-C H OH R -co-c .H XC H -cH -c F -o-HCo p p 14 k 2 f p at k 2 2 p t: f

x H CH CF-CH R doc H CH 0H CH c a o H -co-c H 42 2k 2 f k 2X 2 a -w. f

and 8" represent respectively mono, di and higher mercaptans:

a. Mono-mercaptans BSH, wherein B may be:

alkyl with l to 24 carbons and preferably 6 to 18 Polymercaptans with 8to 10 mercapto groups can be prepared by esterifying tripentaandtetrapentaerythritol with thioglycolic and thiopropionic acid. Insteadof pentaerythrito] or homologs thereof, other polyhycarbons, cycloalkyl,arylwith 6to 24 carbons, aral- 5 droxy compounds such as sorbitols etc.may be emkyl with 7 to 24 carbons, and -alkylene-CO ployed to synthesizeuseful polymercaptans. alkyl,aryl, or aralkyl. Another most useful classof polymercaptans are de- Preferred monomercaptans of the above type arefor rived from monoor polyepoxides and thioglycolic or example: relatedacids according to the following equation:

Hexyl, octyl, decyl, dodecyl, hexadecyl and octadecyl mercaptan,thiophenol; thionaphthol; benzyl, I 3-phenylpropyl, triphenylmethyl,dodecylbenzyl and cyclohexyl mercaptan, octyl thioglycolate; di-'C'OOCCHZSH octyl thiomalate. Of special interest are also fluori- Onated alkyl mercaptans with 4 to 24 carbon atoms C C OOCCH2SH of WhlCh 3to 18 of the carbon atoms are fluori- 1 I nated. Such mercaptans withthe formula QR,C H Cl-l SH, wherein 20 as described in the followingpatents.

Q is hydrogen, chlorine or fluorine and R, is perfluoroalkylene with 2to 18 carbons and k is zero to 10 FP 1,103,764, US. Pat. No. 2,992,210

are described in the following US. Pat. Nos:

Commercially available monoor polyepoxides from which usefulpolymercaptans can be derived are deg g gigf g ggyggg 2-965-67713,083,849; scribed in Encyclopedia of Polymer Science and Technology,Volume 6, pages 209-271(John Wiley and Sons, Inc. 1967) xgz fgigii gperfluoroalkyl mercaptans of the 3 A specific example is given below:

b. Dimercaptans B-(SH) wherein B may be: al-

kylene; alkylene-O-alkylene-; alkylene-S-alkylene; alkylene-CO-alkylene-O C-alkylene, cyclohexyl- CH CHCH OCH CH O-CH CH- CH ene,phenylene, naphthylene, phenylenedimethylene, biphenylylene,phenylene-O-phenylene, 0 O1 phenylene-Sphenylene, l HSCHZCOOH Preferreddimercaptans of this type are:

1 ,2-ethanedithiol; 1 ,4-butanedithiol, 1 ,sj

octanedithiol; 2,2-oxydiethanethiol, 2,2'-thiodiea I thanethiol; Iethylene-bis-thioglycolate, 40 HDCHECOOCQCIWHZCCFQethylene-bis-thiopropionate, 3,4- SCEX; COO 2 dimercaptotoluene,xylylenedithiol, hydroquinonedithiol, biphenyl-4,4'-dithiol,

phenoxybenzene-4,4'dithiol.

c. Polymercaptans B (SH) 10 Other useful polymercaptans are: Mercaptotermiare more complex mercaptans and most important are: nated oligomersor polymers such as mercaptan termiesters of thioglycolic andmercaptopropionic acid and nated polybutadiene sold by B. F. GoodrichChemical polyhydroxy compounds with 3 to 10 hydroxy groups Company underthe brand name of Hycar MTB, or as the following examples show: MTBN forwhich the following properties are given:

Hycar MTB Hycar MTBN (Hycar 2000x158) (Hycar l30OXl0) PolybutadieneButadiene-acrylonitrile with mercaptan copolymer with mercaptan terminalgroups terminal groups Mercaptan content, 2.8 3.85

Bound acrylonitrile, 24.0

Specific gravity, .93 .98

Brookfield viscosity, 20,000 35,000

at 27C., cps

Molecular weight, M" 3,000

Dipentaerythritol hexathioglycolate Dipentaerythritol hexa(3-mercaptopropionate) t =ECHCOOCH2R 12 c cis or trans All adducts oftypes I, Ia and II, IIa, IIb are characterized by having two or threecloselypacked R groups per reacted SH group in the adduct molecule. Thisfact is most important since close packed pairs or triplets of R groupsin a molecule give considerable higher oil repellency ratings ifcompared with a molecule containing isolate R groups, i.e., R groupswhich are sepa- Adduct derived from a R malea.te

Or fumarate rated by one or more backbone carbons. For this reason it ismost important that at least one of the substituents R, R or R in theesters of type III CH COOCl-l R Adduct type II C [CH OOCCH SCHCOOCH FtCH COOCH average 2 iamoocucmsal 2 Adduct type I (mixture) is R A or RACl-I as defined earlier. a, ,B-unsaturated esters where R, R and R arehydrogen or methyl, as is the case for perfluoroalkyl acryla tes ormethacr'ylate, give adducts with considerably lower oil repellencies forthe reason explained if compared on an equal fluorine on fabric basis:

Adcluct derived from a R -acrylate or metha rylate e.g. 2 c ucoocn ne.g. 2CH =CHCOOCH R cncooca n f HS-B-SH HS-E-SH cn coocn n cn coocu ncncooon a CH2 S T B B sncoocn n CH2 sn coocn n cn coocu a also: Two (orthree) Sl-l-group.

The addition of hydrogen sulfide or mercaptans of type IV to a,B-unsaturated diand triesters of type III is accomplished either by abase or free radical cataly SIS.

The base catalyzed addition reaction of hydrogen sulfide or mercaptansto ,B-unsaturated esters is well known and described in detail in:

Houben-Weyl, Methoden der Organischen Chemie, Volume 9, pages 123 to 126(George Thieme Verlag, Stuttgart, 1955) The preferred bases recommendedfor such additionreactions, in amounts from 0.01 to 2% at temperaturesvarying from room temperatures to 100C, are generally strong inorganicor organic bases such as:

Sodium or potassium methoxide or ethoxide, benzyltrimethylammoniumhydroxide, piperidine, or pyridine.

It was found, however, that the mercaptan or hydrogen sulfide can beadded to a, B-unsaturated diand triesters of type III with very weakorganic bases such as tertiary amines, as for instance:

triethylamine N-methylmorpholine triethylenediamineN,N-dimethylpiperazine N-ethylmorpholine tetramethyl-l ,4-butane-diaminediethylcyclohexylamine dimethylethanolamine dimethylethylaminediethylmethylamine The use of such weak bases has many advantages, suchas the reduced formation of colored byproducts; the possibility ofleaving the weak base in the final product simplifies the work-upprocedure and reduces costs; little or no reaction occurs with solventssensitive toward strong bases such as ketones or esters.

It is also possible to use free radical initiators or U.V. light for theaddition of hydrogen sulfide or mercaptans of type IV to diand triestersof type III. This is possible because the ditriesters of type III are incontrast to acrylic esters, very reluctant toward homopolymerization. Asuitable catalyst may be any one of the commonly known agents forinitiating the polymerization of vinyl monomers such as azo-initiators,(e.g., azobisisobutyronitrile) or aliphatic and aromatic acyl peroxides,e.g., decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, dialkylperoxides e.g., t-butyl peroxide, cumyl peroxide; or hydroperoxides,e.g., t-butylhydro peroxide, cumene hydroperoxide, or peresters andperoxycarbonates, e.g., t-butyl perbenzoate.

The addition of hydrogen sulfide or the mercaptans to the diandtriesters of type III is usually carried out All El -groups present asisolated singlets,

lower repellency;

Just one R group is introduced per SH-group.

in a solvent in which the reactants and preferably also the adduct aresoluble at the reaction temperature employed. Suitable solvents arealiphatic or aromatic hydrocarbons such as heptane, benzene, toluene,etc; chlorinated or fluorinated aliphatic or aromatic hydrocarbons suchas methylene chloride, chloroform, methyl chloroform, carbontetrachloride, trichloroethylene, perchloroethylene, Freons such as1,1,2- trifluoro-l,2,2-trichloroethane, etc., chlorobenzene,benzotrifluoride or hexafluoroxylene, ketones, esters and ethers such asacetone, methyl isobutyl ketone, ethyl acetate and higher homologs,dialkyl ethers, tetrahydrofuran, ethylene glycol monomethyl or monoethylether, ethylene glycol dimethyl or diethyl ether, and mixtures of theseketones, esters or ethers with wa ter. If one of the components (i.e.hydrogen sulfide, mercaptan or solvent) boils below the reactiontemperature, the reaction is desirably carried out in a pressure tube oran autoclave.

It is most preferable for economic reasons to carry out the additionreactions in that solvent from which the adduct will be applied to asubstrate such as textile, paper, leather and the like or which solventcan be utilized for additional reactions to be carried out with theadduct.

The addition reaction is very simple to carry out, i.e. the mercaptanIV, the dior triester III are dissolved at the desired molar ratios in asolvent described above and the catalyst (0.01-2%) is added. Thereaction mixture is kept at a temperature ranging from room temperatureto 100C, preferably under nitrogen until the disappearance of the doublebond of the ester III indicates that the reaction is complete. Othermeans of following the reaction are GC (gas chromatography), titrationof free mercapto groups or TLC (thin layer chromatography). Requiredreaction times depend on reaction temperatures and amounts and kind ofcatalysts employed and may range from 5 minutes to 24 hours. To obtainproducts free of discoloration it is preferred to work at reactiontemperatures below C, preferably 40to 60C. If required, the additionproduct can be isolated by evaporating the solvent and catalyst (lowvolatile catalysts such as triethylamine are preferred) and be purifiedemploying crystallization, precipitation or distillation procedures.

The synthesis method for the novel compounds as described earlier isusually the preferred one. It is however possible to obtain the sameproducts by adding hydrogen sulfide or mercaptans of type IV to the freea, B-unsaturated diand tri-acids and carrying out the esterification asa last step as the following specific example shows:

HOOC H HOOC H C C H Sexcess .CH-C-SH base 7 l y H COOH H 0005 Freemercapto group containing adducts of type I or Ia are of specialinterest as chain transfer agents in the free radical polymerization ofvinyl and related monomers. By acting as chain transfer agents in themanner of all mercaptan, adducts of type I, la are incorporated into thepolymer chain. This use of the disclosed novel mercaptans is found inFCR-25.

The novel adducts are useful in many ways:

They can be applied to substrates such as textiles, paper, leather,wood, metallic surfaces and the like providing oil and water repellencyto the treated substrates at extremely low add-ons. As shown in theexamples,

good repellency ratings are obtained with as little fluorine as 0.04 to0.12% by weight of the substrate. Besides oil and water repellency, theadducts show excellent fastness properties such as wash and drycleanfastness, abrasion resistance and good drysoiling properties. This isespecially true in the case of adducts of type I having free mercaptogroups which are, in many cases, able to'react with the substrate orextenders. The novel adduct may be applied to the various substrates byvarious coating techniques, such as dipping, spraying, brushing,padding, roll coating, and the like.

The adduct can be applied from a solvent and preferably from a solventin which it was prepared for economical reasons. I

The adducts may also be applied from an aqueous system if either theadduct solution is water miscible or the adduct solution has beenpostemulsified, employing emulsifiers and emulsification techniquesknown in the art. It is understood that the novel adducts can be appliedin combination with other finishes such as extenders, softeners, handbuilders, permanent press resins, catalysts and the like.

Besides being useful per se as soil repellent finishes, which arecorrelated to oil and water repellency, the novel adducts of type I areof interest as intermediates for the synthesis of novel R groupcontaining polymers and addition or condensation products.

Since the novel adducts have little or no film-formin g properties it isadvantageous to apply them to substrates in combination withfilm-forming polymers or copolymers, as used for instance, for textilepigment printing and textile finishing in general. If the novel adductsare applied from a solvent, then the polymeric extenders are dissolvedin the same or a compatible solvent and co-applied to the substrate. Inthe case where a post-emulsified adduct-solution is applied from anaqueous medium, the preferred extenders are aqueous polymer dispersionswhich are miscible with the postemulsified adductsolutions.

Polymers useful for such blends, include for example, but withoutlimitation, polymers and copolymers of alkyl arcylates and alkylmethacrylates, such as methyl methacylate, ethyl methacrylate, isobutylmethacrylate, hexyl methacrylate, and n-octyl methacrylate. Particularlysuitable polymers are poly(methyl methacrylate), poly(isobutylmethacrylate) and poly(n-octyl methacrylate). Also useful are polymersand copoly- RCH CH OOC H i -QELE Q l transesterfication CH-S-SH COOCFCHgRf mers of acrylic acid, methacrylic acid, styrene, alkyl styrene,butadiene, 2-methyl-l,3-butadiene, 2-chloro- 1,3-butadiene; polymers andcopolymers of vinyl esters such as vinyl acetate, vinyl butyrate, vinyllaurate, vinyl stearate, vinyl Z-ethylhexanoate; polymers and copolymersof vinyl halides and vinylidene halides, such as vinyl chloride,vinylidene chloride, vinyl fluoride, vinylidene fluoride; polymers andcopolymers of allyl esters such as allyl propionate, or allyl caprylate;polymers and copolymers of vinyl ketones, such as vinyl methyl ketone,vinyl ethyl ketone, and the like;

polymers and copolymers of vinyl ethers such as methyl vinyl ether,cetyl vinyl ether, and the like; polymers and copolymers of acrylamide,methacrylamide, N-methylol acrylamide, N-methylol methacrylamide,N-isopropyl acrylamide, acrylonitrile and methacrylonitrile.

For example, from about 20 to 97% by weight of poly(methyl methacrylate)blended with the polymer composition of this invention provides veryuseful coating compositions which retain surprisingly high repellencyratings even though the relative amount of fluorinated polymer is verylow.

A preferred class of extender polymers for the dispersion polymers ofthe present invention, particularly for textile applications, isdisclosed in U.S. Pat. No. 3,349,054. These extender polymers give softfinishes that are light stable and help to impart excellent washand-dryclean fastness to finishes derived from adducts described in thisinvention.

Of course, it is understood that besides application to textiles, thecoatings of the fluorinated polymer compositions of the presentinvention are useful in providing oil and water repellent coatings forleather, paper, wood, masonry, metals, plastics, glass, paintedsurfaces, and the like. A very significant advantage of the polymercompositions of the present invention is that they form effective oilrepellent coatings at relatively very low fluorine levels on thesubstrate. In other words, on a given weight basis, the fluorine contentof the polymer compositions of this invention exhibits more effectiverepellent properties than the same level of fluorine in other polymercompositions previously utilized in the art.

A further advantage of the polymer compositions of this invention isthat they may not require a separate curing or heating step, but canprovide excellent repel lent properties after drying in air.

ADDUCT SYNTHESIS Mercaptans employed for the synthesis of Adduct I ofthe present invention are listed in the following Table 1. They are allcommercially available with the exception of the 1,1,2,2-tetrahydroperfluorodecyl mercaptan, which was prepared using aprocedure as described in U.S. Pat. No. 3,544,663.

R esters of type III used for the adduct syntheses are tabulated inTable 2.

EXAMPLE 1 Bis( 1 ,l-dihydroperfluorooctyl) (octadecylthio)succinate,

Bis(l,l-dihydroperfluorooctyl) fumarate (4.4g, 0.005 mole, Example A),n-octadecyl mercaptan (1.43 g, 0.005 mole, Aldrich), triethylamine(006g), and chloroform (24g) were charged into a reaction flask andstirred for 18 hours at 55C, after which time TLC- analysis showedcomplete reaction. The solvent was stripped off in a rotary evaporatorand the residue crystallized twice from an acetone-methanol mixtureyielding 5.1g (88% yield) of white, flake-like crystals with a mp of4243C. The NMR showed proton resonances at 80.85, 3 protons in anapparent singlet, QLl (Cl-l 81.25, 32 protons in a multiplet 1CH CH82.53.l5, 4 protons in overlapping multiplets, C H Ql SCl-l(Qfl -)COO;83.7, 1 proton in a doublet of doublets, S( ILlCl-l 84.6, -4 protons ina triplet -(-OCH CF )X2. TLC analysis showed the adduct to be pure (onespot) and NMR, IR and elemental analysis was consistent for thestructure.

Analysis for C ,,H F O S: Calc. C, 39.1 Found C, 39.2

EXAMPLE 2 Bis( 1,1 ,2,2-tetrahydroperfluorodecyl) (octylthio)succinate,

fumarate tion was unreacted bis(1,1,2,2-tetrahydroperfluorode- 7 cyl)fumarate. The filtrate was stripped of the solvent on a rotary filmevaporator and the oily residue, which solidified on standing wasredissolved in benzene and was passed through a column of 6g of neutralaluminum oxide (activity I). The first 10 ml portion of benzene washcontained unreacted octyl mercaptan. The desired product was obtained inthe following ml portion of benzene wash. The benzene was stripped offand the product was crystallized from hexane. The purified whitecrystalline product (0.7g) possessed a mp of 404lC.

The NMR spectrum showed proton resonances at 80.9, 3 protons in anapparent singlet, C H -(Cl-l 81.1 1.85, 12 protons in a broad resonance,'t-CH 82.1 3.0, 8 protons in overlapping multiplets, -CH- Z CH2S-CH(QEZCOOCH2Q{2C3FI- )COOCH C H C F 83.62, 1 proton in a doublet ofdoublets, SQ-l(Cl-l -)COO; 84.4, 4 protons in overlapping triplets,-1O(ll CH )X2.

These data are consistent with the structure of the adduct.

Analysis for C H Fm i EXAMPLE 3 Bis( l l ,2,2-tetrahydroperfluorodecyl)(1 ,1 ,2,2-tetrahydroperfluorodecylthio )succinate,

Bis( 1,1,2,2-tetrahydroperfluorodecyl) fumarate (2.016g, 0.002 mole,Example B), l,l,2,2-tetrahydroperfluorodecyl mercaptan. (0.960g, 0.002mole), triethylamine (003g) and methyl chloroform (8.2g) were sealed inan ampul under nitrogen and kept at 60C for 7 hours. After cooling, theadduct precipitated, was filtered and recrystallized from methylchloroform. A total of 2.3g (77% yield) of pure, white crystals with amp of 69-69.5C were obtained The NMR showed proton resonances at82.l3.2, 10 protons in unresolved overlapping signals, C F CE Q 52 mQZZQE B U) zQL 2 e 11; 83.75, one proton in a doublet of doublets, SCl-l-COO; 84.5, 4 protons in a triplet, 2X(COOQH CH These data are consistentwith the structure of the adduct.

Analysis for C H F Q I Calc.: C, 27.4

(2.313g; 0.002 mole, Example I), 1,1,2,2-tetrahydroperfluorodecylmercaptan (0.960g; 0.002 mole), triethylamine (0.6g) and methylchloroform (10g) were sealed in an ampul under nitrogen and kept at60C-for 16 hours. The solvent was stripped off and the residue wascrystallized twice from benzene, yielding 2.9g (89% yield) of whitecrystals, mp of 69-69.5C. The NMR showed proton resonances at 8l.663.1,22 protons in complex overlapping signals, c F CL-l cjj lCfi2 1(Q z)22)2 B 11- ]COOCH ((ll S(Qll C F 83.69, one proton in a doublet ofdoublets, SCl-lCOO; 84.22, 4 protons on overlapping triplets, 2X(COOQ' lCl-l These data are consistent with the structure of the adduct.

Analysis for Q E-1 5,0 8

Calc. C, 2 .66; F,

9.35; H, I Found C, 29.24; H, 1.

EXAMPLE Bis[ l l-(perfluoroisopropyU- l O-undecenyl] (1,1 ,2,2-tetrahydroperfluorodecylthio)succinate,

Bis[ l l-(perfluoroisopropyl)- IO-undecenyl] fum arate (1.5 1 3g, 0.002mole, Example J), 1,1 ,2,2-tetrahydroperfluorodecyl mercaptan (0.960g,0.002 mole), triethylamine (0.06g) and methyl chloroform 10g) weresealed in an ampul under nitrogen. The ampul was then heated at 60C for16 hours. The pale yellow solution was then stripped of solvent and theresidual oil was redissolved in benzene. The solution was passed througha column of 6g of neutral aluminum oxide (activity I). The first 50 mlfrom the column were collected and were stripped of benzene. The productwas obtained as a yellow oil (1.9g) in a 77% yield. A VPC check showedthe product to be free of starting materials. The NMR showed protonresonances at 81.25, 28 protons in a singlet, +CH2+7X2; 81.8-3.1, 10protons in unresolved overlapping signals, C F, (ll C j S- CH[Q lCOOCl-l (Cl-l Q l CH--CH-l-; COOCH (CH -QH CH=CH; 83.64, 1' proton in adoublet of doublets, SC H (CH '+COO; 84.1, 4 protons in overlappingtriplets, +O C ll CH X2; 85.4, 2 protons in undetermined broad signals+CH=C HCF+ X2; 86.32, 2 protons in triplets of a doublet; +CH Ql-lllCF-)- X2.

These data are consistent with the structure of the adduct.

Analysis for C H F O (259.48g; 0.04 mole, Example C), n-octadecylmercaptan (12.87g; 0.04 mole, Aldrich), triethylamine (0.25g) andtetrahydrofuran (200g) werecharged into a reaction flash and kept at 70Cfor 72 hours after which time conversion was complete according to IRanalysis. The solvent was then stripped off and the adduct purified byprecipitating the adduct-benzene' solution into twenty times an excessof methanol and 43.7g (84.4% yield) of a white powder, mp 596lC was obtained. The fluorine analysis obtained indicated that the composition ofthe different R -esters did not change in the adduct.

Analysis for Calc.*: F. 49.50 Found F. 50.59 *Calculated from F-contcntof R fumamte. Example C EXAMPLE 7 Bis(1,1,2,2,-tetrahydroperfluorodecyl) mercaptosuccinate,

Thiomalic acid (1.2g, 0.008 moles); l,l,2,2,-tetrahydroperfluorodecylacetate (12.65g, 0.0025 moles), and p-toluenesulfonic acid monohydrate(0.2g) were magnetically stirred and heated to -185 in a nitrogen streamfor 22 hours. Acetic acid was removed in a Dean-Stark trap and confirmedby infra-red analysis. The reaction product was worked up by preliminarydistillation in a Hickman molecular still at -200/.005 mm. followed bytwo recrystallizations from methyl chloroform, yielding white crystalswith a mp of 68.068.7. The NMR confirmed the postulated structure andshowed proton resonances at 82.2, 1 proton, SH; 81.6-15.1, 6 protons,undetermined multiplicity, 2( Ifi R,, fi CO; 83.75, 1 proton, multiplet,SH-Qfi; 84.4, 4 protons, multiplet,

2 fiogg on Analysis for C l-1 5 0 5:

Calc. C, 27.69; H, 1.16; Found C, 28.06; H, 1.18

EXAMPLE 8 Bis( l ,1,2,2,-tetrahydroperllluorodecyl)(triphenylmethylthio)-succinate,

CSCHCOOCHZCHZCBFH ca eooc i cng(3 F mostly of unreacted bis(1,1,2,Z-tetrahydroperfluorodecyl) fumarate. The filtrate was thenstripped of solvent and the residue was crystallized twice from heptane.The purified product (0.9g) was obtained as white crystals, with a mp of6263.5C. A TLC check showed a single spot for the product. The NMRshowed proton resonances at 81 .52.2, 2 protons in the apparent 8 lineAM pattern of an AMX system (12 lines-see 83.22), SCHC;H 822-285, 4protons in an unresolved pattern (-CH CH C F17+X2; 83.22, 1 proton in adoublet of doublets, --SQl -Cl-l 84.25, 4 protons in overlappingtriplets, +OQE CH )XZ; 87.07.65, 15 protons in a complex pattern, (C l-l)-X3.

A trace impurity was evident at 86.8, due to unreacted -(OOCQil=t" llCOO-)-z These data are consistent with the structure of the adduct.

Analysis for C H F O S:

Calc. C, 40. Found C, 39.

EXAMPLE 9 Bis 2-(N-ethyl-perfiuorooctanesulfonamido )ethyl]1,1,2,2-tetrahydroperfluorodecylthio)succinate,

Bis[2-(N-ethyl-perfluorooctanesulfonamido)ethyl] fumarate (2.445g, 0.002mole, Example D), 1,1,2,2-

I tetrahydroperfluorodecyl mercaptan (0.960g, 0.002

mole), triethylarnine (006g), and methyl chloroform (10g) were sealed inan ampul under nitrogen. The ampul was heated at 60C for 24 hours. Acrystalline product formed in cooling; this was filtered and trituratedwith chloroform. One gram of a mp of 106l08 was recovered. The motherliquor was evaporated and the residue crystallized from a solventmixture of 3 parts of hexane and 1 part of chloroform. One gram of awhite crystalline product was isolated having a mp of 778 1C. A TLCanalysis showed the product to contain a trace impurity. The NMR showedproton resonances of 81.25, 6 protons in a triplet, -NCH C +H 81 .6-40,protons in unresolved and overlapping signals, C F gl glj sgL-flQLXCOOCH QE NQE CH )SO COOCH QE N(( ZI CH )SO 84.25, 4 protons inoverlapping triplets, -(-O C I l Cl-l )X2.

These data are consistent with the structure of the adduct.

Analysis for C38H25F51N2OBS3;

Calc. C, 2 Found 1 C, 2

EXAMPLE 10 Tetrakis( l ,1,2,2-tetrahydroperfluorodecyl)(tetramethylenebisthio)disuccinate,

Bis( 1,1,2,2-tetrahydroperfluorodecyl) fumarate (3.024g, 0.003 mole,Example B), butanedithiol (0.183g, 0.0015 mole), triethylamine (0.1g)and methyl chloroform (10g) were sealed in an ampul under nitrogen. theampul was then heated at C for 24 hours. The solvent was then evaporatedand the wax-like residue was crystallized from a mixture of hexane andacetone. The product was obtained as a white powder having a mp of60-6lC in yield (2.42g). A small fraction of this was recrystallizedfrom the hexane-acetone mixture to a mp of 60 61C. A TLC analysis showedthe product to be a single component. The NMR showed proton resonancesat 815-185, 4 protons in broad singlet, CH (C H CH 82.03.0, 16 protonsin unresolved, overlapping multiplets, [CH E SCPK(E COOCH C F, )COOCH Cfl C F 83.63, 2 protons in a doublet of doublets, (SQECHQXZ; 84.4, 8protons in overlapping triplets Frog 2CH2)X4.

These data are consistent with the structure of the adduct.

Calc. 9. Found C, 29.

EXAMPLE 1 l Tetrakis( 1,1,2,2-tetrahydroperfluorodecyl) [thiobis(ethylenethio ]disuccinate,

S H CH SCHCOOCH CH C F CH2COOCH2CH2C8F17Bis(1,1,2,2-tetrahydroperfluorodecyl) fumarate (4.032g, 0.004 mole,Example B), 2,2-thiodiethanethiol (0.309g, 0.002 mole), benzyltrimethylammonium hydroxide [0.05g (Triton B,35% in methanol)], andmethyl chloroform (15g) were sealed in an ampul under nitrogen. Theampul was heated at 60C for 24 hours. The solvent was then evaporatedand the residue was dissolved in hot hexane. An orange oil separatedalmost immediately. The still-warm hexane layer was decanted and allowedto cool further. A white crystalline product formed which was filtered,then slurried with warm chloroform. The insoluble material which wasisolated, was unreacted bis(1,1,2,2-tetrahydroperfluorodecyl) fumarate(mp 9295C, 0.6g). The filtrate was concentrated and diluted with hothexane. On cooling 1.35g of product, mp 6466.5C, crystallized and wasfiltered. The white powder was pure (one spot) by TLC analysis. Theorange oil, which had solidified in the meantime, was then heated with2g of acetone and 5g of hexane. An oil layer remained; the solvents weredecanted, cooled and 0.4g ofa white powder (mp 677 1C) separated. A TLCanalysis showed this to be the same as the previously isolated product(mp 6466.5C). A total of 1.75g of product was isolated. The NMR showedproton resonances at 81.8-33.1, 20 protons in unresolved signals, {-SCfiC ll SCH(C lj- COOCH QE C F )COOCH Cil C F h; 83.69, 2 protons in adoublet of doublets, (SC flCH )X2; 84.36; 8 protons in overlappingmultiplets +OCE CHQX4. A trace impurity was evident at 86.8, due tounreacted OOCC I l=C LlCOO-.

These data are consistent for the structure of the adduct. 1

(4.8g, 0.0048 mole, Example B), glycol di(3-mercaptopropionate) b.p.-144/ 1 mm (0.57g, 0.0024 mole, Evans Chemetics Inc.), triethylamine(0.027g), and methylene chloride (10g) were charged into a pressurebottle and agitated for 16 hours at 50C. Infrared analysis indicated noresidual fumarate unsaturation and the solvent was stripped off in arotary evaporator. The residue was crystallized three times from methylchloroform (70% yield) to yield white crystals with a mp of 69.470.1C.The NMR showed proton resonances at 82.0-3.3, 20 protons, undeterminedmultiplicity,

8335-39, 2 protons, doublet of doublets,

84.154.65, 12 protons, undetermined multiplicity,

3 9 lCOQj CH CF 2CH OC These data are consistent for the postulatedstructure.

Analysis for C H F O S Calc. C, 29.56; Found C, 29.68;

EXAMPLE 13 Hexakis( 1,1 ,2,2-tetrahydroperfluorodecyl) [ethylidynetris(methyleneoxycarbonylethylenethio trisuccinate,

CH C (CH OOCCH CH SCHC OOCHZCH CgFl 7 Bis( l l,2,Z-tetrahydroperfluorodecyl) fumarate (4.84g, .0048 moles, Example B),trimethylolethane tri(3-mercaptopropionate) (0.62g, .0016 moles), andtriethylamine (003g) are dissolved in 10g of methylene chloride andreacted under nitrogen for 16 hours at 50 in a pressure bottle.Additional methylene chloride (20g) is added to facilitate transfer andthe solution is cooled to 0 and filtered. The crystallized tri-adductweighs 5.3g (96% yield), has a mp of 7981C and shows no residualunsaturation by infrared spectroscopy. lt is recrystallized from methylchloroform to a mp of 81.982.4C and its purity confirmed by NMR. Thecompound showed NMR proton resonances at 81.0, 3 protons, C l'1 C; 81.853.2 30 protons, undeter' mined multiplicity 3(CC l i CF 3CQl l C l S,3 Qll CO 83.65, 3 protons, doublet of doublets, 3CH; 84.05, 6 protons,singlet, 3 Ql -l O CCl-I 84.37, 12

I protons, multiplet, 3(CO Qli Cl-l These data are consistent with thepostulated structure.

Analysis for Cg5H54 102 1G 3 Calc. C, 30.30; Found 1 C, 30.24;

EXAMPLE 14 Octakis( 1,1,2,2-tetrahydroperfluorodecyl)[neopentanetetrayltetra (oxycarbonylethylenethio)]tetrasuccinate 1 C(Cl-1 OOCCHZCHZSCHCOOCHQCHZCsFl 7 Bis( 1 l,2,2-tetrahydroperfluorodecyl) fumarate (0.003 moles Example B),pentaerythritol 83.7, 4 protons, 4 SC H; 84.04.7, 24 protons, 12 Qflz-Analysis for C g ms 24 -1 Calc. C, 30.0 Found C, 29.9

EXAMPLE the reaction mixtures were removed and the free SH- contentdetermined iodimetrically. The titration results Addition Products (2/l)of Bis( l,l,2,2tetrahydroand the disappearance of the R -fumarate doublebond fl rodec l) at 1,300-l.310 cm indicated that the desired mixedHSCHZCHQCOOCH ---C rl OOCCH CH S?HCOOCH CH C F 2 (average) ca coocrt crtc r 2 (average) Bis(1,1,2,2-tetrahydroperfluorodecyl) fumarate adductswere obtained quantitatively. After evapora- (20.l2g, .02 moles),pentaerythritol tetra(3-mercaptotion of the methyl chloroform, alladducts were obpropionate) (4.88g, .01 moles), and triethylamine tainedas pale yellowish-white waxes which were not (0.13g) are dissolved in4.5g of methylene chloride and further purified.

R Fumarate Tetra'Mercaptan SH Content Example n g moles g moles calc.found heated at 50 under a nitrogen blanket for 3 hours in 25. EXAMPLES20 23 a pressure bottle. A mercaptan assay of the solution thenindicates 2.4% 81-1 (2.6% theory). The solution is then evaporated on arotary evaporator to yield a white v crystalline residue with residualmercaptan odor. Addition 'iroducts of Bis( l,l,2,2-tetrahydroper- It wascrystallized once from a minimal volume of fluoroalkyl) fumarate andDipentaerythritol methyl chloroform, dried and submitted for analysis.hexa(3- mercaptopropionate),

315 HSCH CH COOCH *CH OCH CHCH OOCCH CH SCHCOOCH CH R 6-n(average) HCOOCH CH R, a J.

b n( average 4O n=3,4,5or6* Analysis for C55H4 FsgO1flS4: The above willonly be a structural representation if grou s a and b are Calc.: C,31.10; 1-1, 1.93; F 51.6 on the same carbon atoms with the sum ofa and bequal to 3 on each Found: C, 31.23; H, 1.69; F, 53 O appropriate carbonatom.

Bis( l ,1,2,Z-tetrahydroperfluoroalkyl) fumarate (Ex- EXAMPLES 16 19ample C), dipentaerythritol hexa(3-mercaptopropion- Addition products ofBis(l,l,2,2-tetrahydroperate) in molar ratios as indicated below, 1%triethylamfluoroalkyl) fumarate and Pentaerythritol ine based on the,weight of the reactants and methyl tetra(3-mercaptoprop1onate),chloroform (4 times the weight of the reactants) were HSCH CH COOCHOtCl-I 0OCCn CH S$HCOOCH CH R 4-n(a"e1age) ca cooczt ca a n( average) nl, 2, 3, or 4 sealed in an ampul under nitrogen and kept in a shaker-Bis(1,1,2,2-tetrahydroperfluoroalkyl) fumarate (Exbath at C for16'hours. After this time, complete reample C), pentaerythritoltetra(3-mercaptopropionaction is obtained as evidenced by disappearanceof the ate) in molar ratios as indicated below, 0.5% of trieth- R-fumarate ester double bond at 1,300l,310 cm ylamine based on the weightof the reactants and and the SH-content as given below. Afterevaporation methyl chloroform (4 times the amount of the reacof thesolvent, the different adduct mixtures were obtants) were sealed in anampul under nitrogen and kept tained quantitatively as yellow-whitesolids with meltfor 15 hours at 45C. After this time, aliquot parts ofing points as shown below.

SH-content g (moles)of g (moles)of in Adduct Melting Range Example n Rfumarate hexa mercaptan culc. found of Adducts,C

A structural representation drawn from these exammole), 1% oftriethylamine based on the weight of the ples would be reactants and 50gof methyl chloroform were sealed in an ampul under nitrogen and kept forhours in a water bath shaker at 60C. After this time the R,- Q Qfumarate double bond at 1,300-1,310 cm has disappeared as shown byIR-analysis and the SH-content, de- Qr' z z -Q 15 terminediodimetrically, dropped to half of the initial g value indicating thatin all cases the reaction was complete. After evaporation of the methylchloroform and I p .triethy1amine, all 2zladducts (average ratio) areobi I ta ined as slightly off white waxes or powders, having a wherein Qis a. -CH OOCCH CH SH or faint mercaptan Odor.

. i (b) --CH OOCCH SCHCOOCH CH R *XAMPLES 31 34 1 Addition products (2to 1) of R itaconate esters and CHECOOCHZCHZRf Pentaerythritoltetra(3-mercaptopropionate) HSCH CH COOCH CH OOCCH CHSCH CHCOX-L R L 2(average) CH COXLR 2 (average) and the sum of (b) totals 3, 4, 5 or 6. Xoxygen or sulfur, L =linkage group and R;= perfluoroalkyl group as shownin Table 3. R itaconates (0.01 mole) as listed in Table 4, penta-EXAMPLES 24 3O 35 erythritol tetra(3-mercaptopropionate) (2.5g, 0.005

moles) were reacted as described in the preceding ex- Addition products(2 to 1) of R -Fumarate esters and amples 24 30. Adducts (2:1 averageratio), as shown Pentaerythritol tetra( 3-mercaptopropionate), in Table4 are obtained in quantitative yields proven by c cn ooccu ca scacox-L-RX oxygen or sulfur, L linkage group and R per- IR-analysis (completedisappearance of itaconate doufluoroalkyl group, as shown in Table 3.ble bonds) and free SH-content. R fumarates (0.01 mole) as listed inTable 3, penta- All adducts were off-white powders with a faintmererythritol tetra(3-mercaptopropionate) (2.5g, .005 captan odorrequiring no further purification.

HSCHZCHZCOOCHE TABLE 3 Example R Furnarate 2:1 Adduct (average) ofR,fumarate and N0. Pentaerythritol tetra( 3'mercaptop'ropionate) 24CHCOSCH CH C F, I ['HSCH CH COOCl-1 C-[Cl'i OOCCl-1 CH SC1-lCOSCH CH C,F

Example E i H cOsCl l cl-l C-f 2 =%CHCOOCH CH Cl-1=CHC,F,,,] HSCH C HCOOCH C[CH OOCCH CH SCHCOOCH CH CH=CHC H Example F CH COOCH CH CH==CHC F2 TABLE 3 Continued Example R,-Fumarate I 2: l-Adduct (average) of Rfumarate and No. Pentaerythritol tetr21( 3-mercaptopropionate) Example MCH COSCH CH NHCOC F 3O =[=CHCOOCH CH N(C l-l,=,)SO C, F, --i=-[HSCH CHCOOCH C[CH OOCCH CH SCHCOOCH CH N(C H )SO C,.F

Example cn coocu cn mc n so cn= TABLE 4 Example R ltaconate 2: l-Adduct(average) of R itaconate and No. Pentaerythritol tetra(3-mercaptopropionate) ca coocu cm CH COCCH C F Example D 32CH2=(|ICOOCH2C H OCH CH=CHC F,HSCH2CH2COOCH2]2C{CH2OOCCH2CH2SCH2CHCHZCH2OCH2CH=CHCTFH CH COOCH CH OCHCH=CHC F 2 2 2 2 7 is 2 Example H 1 33 CHZCCOOCH2CHZN(C2H5)SOZCBF,7[HSCH2CH2COOCH2]2C[ CH OOCCH CH SCH CHCOOCH CH N(C l-l;,)SO C F,

CH COOCH CH N(C H )SO C F, 2 2 2M 2 5 2 lFn Example N 34 CHZ=CCONCHZC7FH[HSCH CH COOCH -C[CH OOCCH CH SCH $HCONCH C F CH2CONCHZC7F15CH2CONCH2C7F, 2

Example P EXAMPLE 35 ADDUCT EVALUATION 4 to 1 adduct ofBis(1,l,2,Z-tetrahydroperfluorode- In the evaluations carried out inexamples 36 to 62, cyl) fumarate and Tripentaerythritolocta(3-mercaptounextended adduct solutions and adduct solutionsexpropionate) tended with polymethyl methacrylate to a fluorine con- IHSCH CH COOCH ca ocu cca oca (CH2OOCCHZCHZSCHCOOCHQCHZ 8 17 (average) CHC0OCH CH B l 1 (average) Bis(1,1,2,2-tetrahydroperfluor0decyl) fumaratetent of based on total solids, were applied to cotg, 0.025 moles,Example B); tripentaerythritol ton and dacron test fabrics by a paddingprocess in such octa(S-mercaptopropionate), (6.73g, 0.0063 moles) a wayto leave 0.04, 0.08, 0.12 and 0.2% fluorine deand triethylamine (0.32g)were dissolved in 60g of aceposited on the fabric. The fabric wasevaluated after air tone and sealed under nitrogen in an ampul. After 16drying and after curing in a hot air oven at 150C for hours in awaterbath shaker at 50C, the adduct solu- 3 minutes. The use ofpolymethyl methacrylate is tion was evaporated to dryness to yield awaxy solid strictly to illustrate the usefulness of a polymeric exwith amelting range of 103 to l 1 1C, having 2.3% free tender, but otherfilm-forming polymers and textile fin- SH-groups (theory 2.55%)determined iodimetrically ishes as listed before could be employed aswell.

and no residual fumarate double bonds as shown by IR- Cotton and dacronwere used as a test fabrics be analysis. cause cotton and dacron aregenerally most difficult to render oil and water repellent. It istherefore understood that the novel adducts and adduct-blends work asAnalysis for C H F O S well and better on easier to treat fabrics suchas wool,

Cale. C, 31.72; H. 8 Found I C 3mg; H 7 tpggyizlrgndes, polyacrylics,cellulosics and blends of such American Association of Textile Chemistsand Colorists. Ratings are given from 50 (minimum) to 100 (maximum).

The AATCC Oil Rating was determined according to Standard Test Method 118-1966T of the American Association of Textile Chemists and Colorists.Ratings are given from 1(minimum) to 8(maximum). A commonly acceptedlevel on soil repellent fabrics in the US. is an oil repellency of 3 4.The soil release properties were determined according to AATCC StandardTest Method 130-1969. Ratings are given from 1(minimum) to 5(maximum).

The drycleaning was carried out according to AATCC Standard Test Method86-1970.

The home washes were carried out in a Kenmore washing machine, Model 600at 120F, employing 45g of the detergent Tide XK per washload.

The mentioned AATCC Tests are listed in the Technical Manual of theAmerican Association of Textile Chemists and Colorists, Volume 46,Edition 1970.

EXAMPLES 36 to 51 EXAMPLES 52 to 55 2% solutions of adducts examples 16and 17 in methyl chloroform Freon 113 (2:1) and of adducts examples 18and 19 in methyl chloroform-acetone (2:1) were applied to cotton aloneand in combination with polymethyl methacrylate in such a way that0.04%, 0.08% and 0.12% of fluorine were deposited onto the fabric, usingmethyl chloroform as a diluent. AATCC oil and spray ratings obtained arelisted in Table 6.

EXAMPLES 56 to 59 10% solutions of the adducts examples 20, 21, 22 and23 were prepared by dissolving the adducts in solvent mixture of methylchloroform-acetone -Freon l 13 (50:37:13). These solutions were appliedto cotton as described in examples 52 to 55 using methyl chloroform as adiluent, and AATCC Oil and Spray ratings were determined as shown inTable 7.

EXAMPLES 60 to 62 Cotton samples which were treated with adductsExamples 16, 17 and 18 according to the procedure of Examples 52, 53 and58. A total. ofO. 12% fluorine was obtained based on the weight offabric. The samples were (a) three times drycleaned or (b) washed threetimes or (c) submitted to a soil release test according to testspecifications, as shown in Table 8. The oil repellency ratings obtainedas shown in Table 8 after drycleaning and washing, indicate that thenovel adducts show signiflcant fastness even at low fluorineconcentrations. The soil release data in Table 8 indicate the noveladducts have good soil release properties.

TABLE 5 Adduct Fluorine AATCC OlL AATCC WATER Example Example in AdductSolvent REPELLENCY REPELLENCY No. No. by wt. System 0.2% F 0.2% F 0.2% F0.2%

Methyl Chloro' 36 1 48.30 form 0 5O 60 Methyl Chloro- 37 2 55.36 form 11 6O 50 Methyl Chloro- 38 3 65.95 germ acetone 1-2 2 60 70 :1 MethylChloro- 39 4 59.86 form 4-5 3 70 0 Methyl Chloro- 40 5 47.47 form 0 0 50Methyl Chloro- 41 6 50.59 form 0 0 70 Methyl Chloro- 42 7 61.99 form 4-55 7O 60 Methyl Chloro' 43 8 53.91 form 1 1 70 Methyl Chloro- 44 9 56.27form acetone 5 5 0 50 1:1 Methyl Chloro- 45 10 60.68 form 6 5-6 90Methyl Chloro- 46 l l 60.22 form 6 5-6 70 80 Methyl Chloro- 47 12 57.81form 6 6 70 6O Methyl Chloro- 48 13 58.27 form acetone 6 6 80 80 TABLEContinued Adduct Fluorine AATCC OlL AATCC WATER Example Example inAdduct Solvent REPELLENCY REPELLENCY N0. N0. by wt." System 0.2% F 0.2%F" 0.2% F 0.2%

Methyl Chloro- 49 14 57.1 1 form acetone 6 6 80 80 1:1 Methyl Chloro- 5O53.00 form acetone 6 5-6 70 70 1:1 Methyl Chloro- 51 50.97 form acetone6 5-6 0 0 "72 fluorine as determined by elemental analysis 'Extendedwith polymethyl methacrylate to 2071 fluorine in total solids.

TABLE 6 Example Adduct Fluorine Drying and AATCC OIL REPELLENCY AATCCWATER REPELLENCY N0. Example in Adduct Curing With Extender" WithExtender" No. by wt. Conditions 0.08%F 0.04%F 0.08%F 0.12%F 0.04% 0.08%F0.12%F

Air dried 6 4-5 6 6-7 60 70 52 16 57.2 3 Min. at 150C 5 4-5 6 6 7O 7O 70Air dried 5 5 6 6-7 0 60 70 53 17 55.2 3 Min. at 150C 4-5 4 6 6-7 50 7070 Air Dried 4 2-3 6 6 0 70 70 54 18 51.6 3 Min. at 150C 3-4 2 6 6 50 7060 Air dried 4-5 4-5 6 6 0 50 70 19 43.3 3 Min. at 150C 4 2-3 6 6 50 0"Extended with polymethyl methaerylate to 20% fluorine in total solidsTABLE 7 Example Adduct Fluorine Drying and AATCC OlL REPELLENCY AATCCWATER REPELLENCY No. Example in Adduct Curing With Extender" WithExtender" No. by wt. Conditions 0.08%F 0.04%F 0.08%F 0.12%F 0.04%F0.08%F 0.12%F

Air dried 5 4 5-6 6 50 60 56 20 56.28 3 Min. at 150C 5 4 5-6 6 50 60 70Air dried 5 3-4 5 6 0 50 50 57 21 53.9 3 Min. at 150C 5 3 5 6 0 50 70Air dried 5 3-4 5-6 6 0 60 70 58 22 52.0 3 Min. At 150C 6 3-4 6 .6 50 5070 Air dried 6 4 5 6 0 50 60 59 23 49.1 3 Min. at 150C 6 2-3 6 6 50 6060 "Extended with polymethyl methacrylate to 20% fluorine in totalsolids.

TABLE 8 Extended" Adduct Example Adduct Test Methods on Cotton, 0.12%FOWF No. Example No. Air dried 3 Min.at 150C Oil Repellency, initial 6-76 After 3 drycleanings 4-5 3 60 16 After 3 home washes" 3 4 Soil ReleaseRating- 3-4 3-4 Oil Repellency after Soil Release 5 6 Oil Repellency.initial 6-7 6 7 After 3 drycleanings 2 1-2 61 17 After 3 home washings2-3 4 Soil Release Rating 3 3 Oil Repellency after Soil Release 4 5 OilRepellency, initial 6 6 After 3 drycleanings 4-5 4-5 62 22 After 3 homewashes l l Soil Release Rating 3-4 3-4 Oil Repcllency after Soil Release2 2 Extended with polymethyl methacrylate to 20% fluorine in totalsolids 'AATCC Test Method 1 18- 1966 T "AATCC Test Method 86-1970 "Homewash in Kenmore washing machine at 1207: F, 45g Tidc XK "AATCC TestMethod -1969 3,886,201 33 34 What is claimed is: wherein m is l, 2, 3 or4. 1. A compound of the formula 4. The compound of claim 3 wherein Rcontains 6 to 12 carbon atoms.

5. The compound of claim 3 wherein AR, is

f $1 5 coocH cH R,.

C Z [SH 1n 6. The compound of claim 1 of the formula: R Q Q 3 R2 m i lQ('3CH OCH C -Q wherein Q Ran and R are hydrogen, methyl, R A or R ACHwherein Q is where at least one of R R and R is R A or R ACH Risa n lklf2tl8carb I Per Y group 0 CH ooccn CH bCHAR or atoms, RA is 2 2 2 O CHAR l --(i O-C H -R b. CH OOCCH CH SH and the sum of (b) totals 3, 4, 5or 6. Z i 7. The compound of claim 6 wherein R; contains 6 to C(Cl-lOOCCl-l Cl-l 12 carbon atoms. C(CH OOCCH -h 8. The compound of claim 6wherein AR, is CH C(CH OOCCH CH I COOCH CH R;. CH C(Cl-l OOCCH 9. Thecompound of claim 1 of the formula:

(HSCH CH COOCH C -(CH OOCCH CH SCH (?HA -R CH -A-R CH CH C(CH OOCCH CH-)3 wherein m is l, 2, 3 or 4. CH CH C(CH OOCCH 10. The compound ofclaim 9 wherein R, contains 6 0i- 2- 2 z')'a. 12 0f to 12 carbon atoms.2- 2 2 2T3 12 11. The compound of claim 9 wherein AR, is k is 1 or 2COOCH CH R;. V

m is at least 1 and thc S O m n 15 3, 4 OT 6 12. An addition product of2moles/l mole ofbis( 1,1- 2. The compound of claim 1 wherein R; contains6 to ,2,Z-tetrahydroperfluorodecyl) fumarate and penta- 12 carbon atoms.40 erylthritol tetra (3-mercaptopropionate) of the for- 3. The compoundof claim 1 of the formula: mula:

(HSCH CH COOCH W C --CH OOCCH CH S -?HAR CH -A-R CH CH COOCH OOCCH CHSi1HCOOCH CH C F 2(average) CH COOCH CH C F 2 (average)

1. A COMPOUND OF THE FORMULA
 2. The compound of claim 1 wherein Rfcontains 6 to 12 carbon atoms.
 3. The compound of claim 1 of theformula:
 4. The compound of claim 3 wherein Rf contains 6 to 12 carbonatoms.
 5. The compound of claim 3 wherein ARf is -COOCH2CH2Rf.
 6. Thecompound of claim 1 of the formula:
 7. The compound of claim 6 whereinRf contains 6 to 12 carbon atoms.
 8. The compound of claim 6 wherein ARfis -COOCH2CH2Rf.
 9. The compound of claim 1 of the formula:
 10. Thecompound of claim 9 wherein Rf contains 6 to 12 carbon atoms.
 11. Thecompound of claim 9 wherein ARf is -COOCH2CH2Rf.
 12. An addition productof 2 moles/1 mole of bis(1,1,2,2-tetrahydroperfluorodecyl) fumarate andpentaerylthritol tetra (3-mercaptopropionate) of the formula: